Redox chemistry, which is frequently encountered in the formation of new bonds and stereocentres, relies on the compatibility of redox potentials. Despite recent advances, achieving a general electrocatalytic cyclic deracemization process without stoichiometric redox reagents remains a formidable challenge. Here we show that electrocatalytic cyclic deracemization of secondary alcohols can be accomplished through sequential iridium-catalysed enantioselective anodic dehydrogenation and rhodium-catalysed cathodic hydrogenation, utilizing metal hydride catalysis. A considerable hurdle arises as stronger hydride donors necessitate parent metal complexes to possess low reduction potentials, resulting in inherent redox potential incompatibility. Nonetheless, we overcame this incompatibility by leveraging a recyclable rhodium-catalyst-modified electrode as the cathode—an accomplishment that homogeneous rhodium catalysis could not achieve. Our approach enables chemoselective stereochemical editing of bioactive compounds with remarkable functional group tolerance. Surface characterization and mechanistic studies showcased the unique advantages conferred by the chemically modified electrode.

在形成新键和立构中心时经常遇到的氧化还原化学依赖于氧化还原电位的相容性。尽管最近取得了进展，但在没有化学计量氧化还原试剂的情况下实现通用电催化循环去消旋化过程仍然是一个艰巨的挑战。在这里，我们表明，利用金属氢化物催化，可以通过连续的铱催化对映选择性阳极脱氢和铑催化阴极氢化来完成仲醇的电催化循环去消旋化。由于更强的氢化物供体需要母体金属配合物具有低还原电位，从而导致固有的氧化还原电位不相容，因此出现了相当大的障碍。尽管如此，我们通过利用可回收的铑催化剂改性电极作为阴极克服了这种不兼容性，这是均相铑催化无法实现的成就。我们的方法能够对具有显着官能团耐受性的生物活性化合物进行化学选择性立体化学编辑。表面表征和机理研究展示了化学修饰电极所赋予的独特优势。